Sulphur dyestuffs



Patented June 15, 1943 UNITED STATES PATENT OFFICE SULPHUR DYESTUFFSWerner Zerweck, Frankfort-on-the-Main-Fechenheim. and WilhelmHechtenberg, Frankforton-the-Main, Germany, assignors to General Aniline& Film Corporation, New York, .N. Y., a corporation of Delaware NoDrawing. Application July 22, 1941, Serial No. 403,574. In Germany July22, 1940 6 Claims.

and

LI V

wherein R stand for an arylradicle, containing at least one and at mosttwo benzene nuclei.

The products corresponding to scheme I generally are named ascoeramidonine compounds, those corresponding toscheme II asdicoeramidonine or dibenzodiazaperylene compounds; both types areobtainable according to the process of British specification No. 7,398of 1901.

The process of sulphurization may be carried out by one of the usualmethods such as by treatment with sulphur and/or sulphur dichloride or apolysulphide solution in the presence or absence of a copper compoundand isolating the reaction product in the usual manner.

The present dyestufis dye the vegetable fibers mostly brownish to oliveto grayish shades of valuable .fastness properties.

In order to further illustrate our invention the following examples aregiven, the parts being by weight and all temperatures in degreescentigrade.

Etcample 1 To a polysulphide mixture of '70 parts of crystallized sodiumsulphide and 40 parts of sulphur 20 parts of coeramidonine of theformula v are added at boiling temperature. The mixture is boiled atabout 118 for some hours under reflux, then the mass is evaporated,subsequently the residue is heated to about 270 and held for about 8hours at 270 to 280. The raw product is dissolved in a mixture of sodiumsulphide and a caustic soda solution and -the sulphur dyestufi thusformed is isolated by acidifying the aqueous solution. It is when dry ablack powder and dyes the vegetable fibers from the sodium sulphide batholive-brown shades. y

Example 2 When starting for the process as described in Example 1 fromthe equivalent amount of 14- methylcoeramidonine of the formula:

and adding 5 parts of copper sulphate to the residue obtained afterevaporisation the formed dyestufi dyes the vegetable fibers brownisholive shades.

Example 3 To a mixture of 12 parts of sulphur and 150 parts of sulphurdichloride there are added slowly at 70 to 80 40 parts of14-(4-aminophenyl) ooeramidonine of the formula:

The mixture is slowly heated to about 150, then boiled for about 1 hourunder reflux and then the mass is distilled until dryness. The residueis thereafter heated to about 270 and held at this temperature for about6 hours. After treatment with a mixture of sodium sulphide and a causticsoda solution the dyestufi is isolated as described above. It is whendry a black powder and dyes the vegetable fibers from the sodiumsulphide r bath dark brown shades.

By adding copper sulphate a dyestufi is obtained which dyes somewhat,more bright shades. The aforesaid 14-(4'-aminophenyl) -coeramid onine isobtainable according to British specifi- (cf. German Patent 272,614) theformed dyestufi dyes the vegetable fibers olive-brown shades Whereas thedyestufi obtained while starting from 12.13-benzocoeramidonine of theformula:

(of. German Patent 246,337) dyes brownish olive shades.

Example 4 gray powder and dyes the vegetable fibers greenish grayshades, whereas the dyestuff derived from nitro-14.15-benzocoeramidonineobtainable by nitrating likewise 14.15-benzocoeramidonine dyesolive-brown shades.

Example 5 obtainable for instance according to British specification No.7,398 of 1901. The mixture is slowly heated to about then boiled forabout one hour in an apparatus provided with a reflux con denser andevaporated to dryness. The residue is then heated for about 6 hours atabout 270 and then dissolved in the usual manner in a mixture of sodiumsulphide and a caustic soda solution. The formed dyestufi is isolatedtherefrom by acidification or blowing in air. It is when dry a blackishgray powder and dyes the vegetable fibers from the sodium sulphide batholive shades of good fastness.

When adding to the aforesaid residue, obtained after the evaporation todryness, 8 parts of copper sulphate, heating the mixture for about 6hours at about 300 and dissolving the reaction mass in a sodium sulphideand caustic soda solution the isolated dyestufi is when dry anolivebrown powder and dyes the vegetable fibers from the sodium sulphidebath olive. shades.

Example 6 Y When starting from the dimethylated derivative of5.6.11-.12-dibenzo-4.10-diazaperylene of the formula:

fast olive shades.

Example 7 To a polysulphide mixture of 56 parts of crystallized sodiumsulphide and 32 parts of sulphur there are added at boilingtemperatures, 20 parts of dinitro-5.6.l1.12-dibenzo 4.10 diazaperyleneobtainable for instance by nitrating5.6.11.12-dibenzol.lfl-diazaperylene with a small excess over thetheoretical amount of nitric acid in the presence of sulphuric acid. Themixture is boiled for some hours at about 118 in an apparatus providedwith a reflux condenser and then evaporated to dryness. The residue isheated at 280 to 300 for about 4 hours. The raw product thus obtained isdissolved in a mixture of sodium sulphide and a caustic soda solutionand the formed dyestufi is isolated as described above. It is when dry agray powder and dyes the vegetable fibers from the sodium sulphide bathbrownish olive shades.

Example 8 A mixture of 50 parts of dinaphtho-4.10-diazaperylene of theformula:

prepared by the action of phosphoric acid in the heat on1.5-di-2'-naphthylaminoanthraquinone and 200 parts of sulphur is slowlyheated to about 270 and the mixture is held for some hours at thistemperature. After having been dissolved in a mixture of sodium sulphideand a caustic soda solution the formed dyestuff is isolated as ablackish powder which dyes the vegetable fibers olive shades.

We claim: I

1. Sulphur dyestuffs obtained by acting with a sulphurizing agent on ananthracene derivative, in the molecule of which the anthracene nucleusis condensed with at least one and at most two nitrogen containingrings, which rings on the other side are connected with arylradiclescontaining at least one and at most two benzene nuclei, which dyestuffsdye the vegetable fibers brownish to olive to grayish shades of valuablefastness properties.

2. Sulphur dyestufis obtained by acting with a sulphurizing agent on ananthracene derivative corresponding with the formula:

wherein R stands for an arylradicle, containing at least one and at mosttwo benzene nuclei, which dyestufis dye the vegetable fibers brownish toolive to grayish shades of valuable fastness properties.

3. Sulphur dyestufis obtained by acting with a sulphurizing agent on ananthracene derivative corresponding with the formula:

sodium sulphide and sulphur on an anthracene derivative correspondingwith the formula which dyestuff dyes vegetable fibers olive brownshades.

5. The sulphur dyestuff obtai-nedby acting with sulphur and sulphurdichloride on an anthracene a sulphurizing agent whichcomprises-amixture derivative corresponding with the formula of sulphurand sulphur dichloride on ananthracene derivative corresponding with theformula which dyestuii dyes vegetable fibers darkbrown 20 which dyestufldyes'vegetable fibers olive shades. shades.

6. The sulphur dyestufi obtained by acting with a sulphurizing agentcomprising a mixture of WERNER ZERWECK. WILHELM HECH'I'ENBERG.

